WO2019216636A1 - 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 - Google Patents

변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 Download PDF

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WO2019216636A1
WO2019216636A1 PCT/KR2019/005482 KR2019005482W WO2019216636A1 WO 2019216636 A1 WO2019216636 A1 WO 2019216636A1 KR 2019005482 W KR2019005482 W KR 2019005482W WO 2019216636 A1 WO2019216636 A1 WO 2019216636A1
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conjugated diene
carbon atoms
modified conjugated
based polymer
group
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PCT/KR2019/005482
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English (en)
French (fr)
Korean (ko)
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이태철
김민수
손기석
김노마
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주식회사 엘지화학
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Priority to US16/754,985 priority Critical patent/US11485800B2/en
Priority to EP19798869.4A priority patent/EP3689926B1/de
Priority to CN201980005076.4A priority patent/CN111212858B/zh
Priority to JP2020514672A priority patent/JP6964184B2/ja
Publication of WO2019216636A1 publication Critical patent/WO2019216636A1/ko

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/08—Epoxidation
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    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
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    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/06—Comonomer distribution, e.g. normal, reverse or narrow
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a modified conjugated diene-based polymer having excellent processability and excellent tensile strength and viscoelastic properties, and a rubber composition comprising the same.
  • a method of reducing the hysteresis loss of the vulcanized rubber In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber.
  • a repulsive elasticity of 50 ° C. to 80 ° C., tan ⁇ , Goodrich heat generation and the like are used as an evaluation index of the vulcanized rubber. That is, a rubber material having a high rebound elasticity at the above temperature, or a small tan ⁇ and good rich heat generation is preferable.
  • the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, and can reduce the movement of the chain end by the binding or modification of the chain end and increase the bonding strength with the filler such as silica or carbon black. It is widely used as a rubber material.
  • solution polymerization SBR When such a solution polymerization SBR is used as a rubber material for tires, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to not only control tire demand properties such as running resistance and braking force, but also increase the glass transition temperature. Proper adjustment can reduce fuel consumption.
  • the solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various modifiers. For example, US Pat. No.
  • 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. It was.
  • the polymerization of the SBR or BR may be carried out by batch (batch) or continuous polymerization, by the batch polymerization, the molecular weight distribution of the polymer produced is advantageous in terms of improving the physical properties, but the productivity is low and There is a problem of poor workability, and in case of the continuous polymerization, the polymerization is continuously made, thus the productivity is excellent, and there is an advantage in terms of processability improvement.
  • the productivity is excellent, and there is an advantage in terms of processability improvement.
  • there is a problem of poor physical properties due to wide molecular weight distribution Thus, in the production of SBR or BR, the situation is constantly being researched to improve both productivity, processability and physical properties at the same time.
  • the present invention has been made in order to solve the problems of the prior art, a modified conjugated diene-based polymer prepared by continuous polymerization and excellent in processability, excellent physical properties such as tensile properties, excellent viscoelastic properties, and the like It is an object to provide a rubber composition.
  • the present invention has a molecular weight distribution curve by gel permeation chromatography (GPC) has a unimodal form, molecular weight distribution (PDI; Provided is a modified conjugated diene-based polymer having a MWD) is 1.0 or more and less than 1.7, comprising a functional group derived from a modified monomer represented by the following general formula (1), at least one terminal containing an aminoalkoxysilane-based modifier-derived functional group:
  • R 1 is hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms
  • X 1 and X 2 independently of one another are hydrogen or —O [CH 2 CH 2 O] a CH 3 , wherein X 1 and X 2 are either —O [CH 2 CH 2 O] a CH 3 , the other One is hydrogen and a is an integer of 1-11.
  • the present invention also provides a rubber composition comprising the modified conjugated diene-based polymer and a filler.
  • the modified conjugated diene-based polymer according to the present invention may have a narrow molecular weight distribution of less than 1.7 while having a unimodal molecular weight distribution curve by gel permeation chromatography, and may have excellent processability and excellent tensile and viscoelastic properties.
  • modified conjugated diene-based polymer according to the present invention may include a modified monomer-derived functional group, the tensile properties and viscoelastic properties can be further improved by including a modifier-derived functional group at at least one end.
  • Figure 1 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene-based polymer of Example 1 according to an embodiment of the present invention.
  • Figure 2 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene-based polymer of Comparative Example 1 according to an embodiment of the present invention.
  • Figure 3 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene-based polymer of Reference Example 1 according to an embodiment of the present invention.
  • Figure 4 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene-based polymer of Reference Example 2 according to an embodiment of the present invention.
  • the term 'substituted' may mean that the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent, and when the hydrogen of the functional group, the atomic group or the compound is substituted with a specific substituent, the functional group, atomic group, or compound
  • One or two or more substituents may be present depending on the number of hydrogen present, and each substituent may be the same or different from each other when a plurality of substituents are present.
  • the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon, and may include linear alkyl groups such as methyl, ethyl, propyl, and butyl; Branched alkyl groups such as isopropyl, sec-butyl, tert-butyl and neo-pentyl; And cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbons including one or two or more unsaturated bonds.
  • alkylene group may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.
  • cycloalkyl group may mean a cyclic saturated hydrocarbon.
  • the term 'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded to each other. hydrocarbons) can be included.
  • the term "monovalent hydrocarbon group” refers to a monovalent substituent derived from a hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group including one or more unsaturated bonds, and an aryl group. It may represent a monovalent atomic group in which carbon and hydrogen are bonded, the monovalent atomic group may have a linear or branched structure according to the structure of the bond.
  • the term 'single bond' may refer to a single covalent bond itself that does not include a separate atom or molecular group.
  • the terms 'derived unit' and 'derived functional group' may refer to a component, a structure or a substance itself derived from a substance.
  • the present invention provides a modified conjugated diene polymer having excellent processability and excellent tensile and viscoelastic properties.
  • the molecular weight distribution curve by gel permeation chromatography has a unimodal form, and the molecular weight distribution (PDI; MWD) is 1.0 or more. It is less than 1.7, it contains the functional group derived from the modified monomer represented by following General formula (1), It is characterized by including the functional group derived from an aminoalkoxysilane type modifier in at least one terminal.
  • R 1 is hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms
  • X 1 and X 2 independently of one another are hydrogen or —O [CH 2 CH 2 O] a CH 3 , wherein X 1 and X 2 are either —O [CH 2 CH 2 O] a CH 3 , the other One is hydrogen and a is an integer of 1-11.
  • the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene monomer, a functional group derived from a modified monomer, and a functional group derived from a modifier.
  • the conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed by the conjugated diene-based monomer upon polymerization, and the modified monomer-derived functional group and the modifying agent-derived functional group are each derived from a functional group and a denaturing agent derived from a modified monomer present in the polymer chain It may mean a functional group derived.
  • the modified monomer-derived functional group may be present in the polymer chain or present at at least one end of the polymer chain, and when the modified monomer-derived functional group is present at one end of the polymer chain, it may be modified at one end of the polymer chain.
  • the monomer-derived functional group may be one in which a denaturant-derived functional group exists at the other end. That is, in this case, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a sock end modified conjugated diene-based polymer that is modified at both ends.
  • the modified conjugated diene-based polymer may be a copolymer including a repeating unit derived from a conjugated diene monomer, a repeating unit derived from an aromatic vinyl monomer, a functional group derived from a modified monomer, and a functional group derived from a modifier.
  • the aromatic vinyl monomer-derived repeating unit may mean a repeating unit formed when the aromatic vinyl monomer is polymerized.
  • the conjugated diene monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 It may be at least one selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom).
  • aromatic vinyl monomers examples include styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, 1-vinyl-5-hexylnaphthalene, 3- (2-pyrrolidino ethyl) styrene, 3- (2-pyrrolidino ethyl) styrene, 4- (2-pyrrolidino ethyl) styrene ethyl) styrene) and 3- (2-pyrrolidino-1-methyl ethyl) - ⁇ -methylstyrene (3- (2-pyrrolidino-1-methyl ethyl) styrene).
  • the modified conjugated diene-based polymer may be a copolymer further comprising a diene-based monomer derived from C 1 to 10 together with the repeating unit derived from the conjugated diene monomer.
  • the diene monomer-derived repeating unit may be a repeating unit derived from a diene monomer different from the conjugated diene monomer, and the diene monomer different from the conjugated diene monomer may be, for example, 1,2-butadiene. .
  • the modified conjugated diene-based polymer is a copolymer further comprising a diene monomer
  • the modified conjugated diene-based polymer is more than 0% to 1% by weight, greater than 0% to 0.1% by weight of the repeating unit derived from the diene monomer, It may be included in more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight, there is an effect of preventing the gel production within this range.
  • the copolymer may be a random copolymer, in this case there is an excellent balance between the physical properties.
  • the random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,000,000 g / mol, or 100,000 g / mol to 800,000 g / mol, the weight average molecular weight (Mw) may be 1,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol, or 100,000 g / mol to 2,000,000 g / mol, peak average molecular weight (Mp) can be 1,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol, or 100,000 g / mol to 2,000,000 g / mol.
  • Mn number average molecular weight
  • the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw / Mn) of 1.0 or more and less than 1.7, or 1.1 or more and less than 1.7, and has excellent tensile and viscoelastic properties within this range. This has the effect of excellent balance between the physical properties.
  • PDI molecular weight distribution
  • the modified conjugated diene-based polymer has a molecular weight distribution curve by gel permeation chromatography (GPC) has a unimodal form, which is a molecular weight distribution appearing in the polymer polymerized by continuous polymerization
  • GPC gel permeation chromatography
  • the modified conjugated diene-based polymer has a uniform characteristic. That is, the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared by continuous polymerization, and may have a molecular weight distribution curve of 1.0 to less than 1.7 while having a unimodal molecular weight distribution curve.
  • the molecular weight distribution curve of the modified conjugated diene-based polymer has a bimodal (or bimodal) molecular weight distribution curve.
  • the growth of each chain may be substantially uniform since the polymerization reaction is started after all the raw materials are added and the growth of the chains may occur simultaneously from the starting point generated by the plurality of initiators.
  • the molecular weights of the polymer chains produced are constant so that they may be in unimodal form with a fairly narrow molecular weight distribution.
  • the start of the reaction and the input of the raw material is carried out continuously, and the starting point at which the reaction is started is different, and thus polymerization Since the initiation varies from the beginning of the reaction, to the beginning of the reaction, to the beginning of the reaction, polymer chains having various molecular weights are prepared when the polymerization reaction is completed.
  • a specific peak does not appear predominantly in the curve showing the distribution of molecular weight, so that the molecular weight distribution curve is wide as a single peak, and even if the chain in which polymerization is initiated is coupled at the end of the reaction, it may be similar to the molecular weight of the chain in which polymerization is initiated at the beginning of the reaction. It is common practice that the distribution curve of unimodal is still maintained since the diversity of the molecular weight distribution can be kept the same.
  • the modification conditions may be controlled to have a unimodal form, but in this case, the whole polymer should be uncoupled or the whole polymer should be coupled. In other cases, the molecular weight distribution curve of unimodal cannot be shown.
  • the molecular weight distribution curve of the modified conjugated diene-based polymer shows a unimodal distribution even when manufactured by the batch polymerization method as described above, when all the polymers are coupled, only polymers having the same molecular weight are present. This may be poor and the compoundability may be poor due to the reduction in functionality due to coupling, which may interact with fillers such as silica or carbon black, and on the contrary, if all of the polymer is not coupled, When the polymer terminal functional groups which have to interact with the filler such as silica or carbon black are more prevalent than the fillers, the interaction between the polymer terminal functional groups is superior to the fillers, and the interaction with the fillers may be hindered.
  • the coupling number is the number of functional groups that can be bonded to the polymer present in the modifier after the modification of the polymer. It is a dependent figure. That is, it represents the ratio of a polymer without coupling between polymer chains and only terminal modification, and a polymer in which a plurality of polymer chains are coupled to one modifier, and may have a range of 1 ⁇ CN ⁇ F, where F is a modifier. In this case, it means the number of functional groups that can react with the active polymer terminal.
  • a modified conjugated diene-based polymer having a coupling number of 1 means that all of the polymer chains are not coupled
  • a modified conjugated diene-based polymer having a coupling number of F means that all of the polymer chains are coupled.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may have a molecular weight distribution curve of unimodal form and a coupling number greater than 1 and smaller than the number of functional groups of the modifier used (1 ⁇ C.N ⁇ F).
  • the modified conjugated diene-based polymer may have a Si content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm by weight, and within this range, modified conjugated diene.
  • the Si content may refer to the content of Si atoms present in the modified conjugated diene-based polymer.
  • the Si atom may be derived from a modifier-derived functional group.
  • the modified conjugated diene-based polymer may have an N content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm based on the total weight, and within this range, the modified conjugated diene-based polymer.
  • the N content may refer to the content of N atoms present in the modified conjugated diene-based polymer, wherein the N atoms may be derived from a modifier-derived functional group.
  • the Si content may be measured by, for example, an ICP analysis method, and the ICP analysis method may be measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV).
  • ICP-OES inductively coupled plasma emission analyzer
  • about 0.7 g of the sample was placed in a platinum crucible (Pt crucible), about 1 mL of concentrated sulfuric acid (98 wt%, Electronic grade) was heated at 300 ° C. for 3 hours, and the sample was After the conversation in the electric furnace (Thermo Scientific, Lindberg Blue M) in the program of steps 1 to 3,
  • step 1 initial temp 0 °C, rate (temp / hr) 180 °C / hr, temp (holdtime) 180 °C (1hr)
  • step 2 initial temp 180 °C, rate (temp / hr) 85 °C / hr, temp (holdtime) 370 °C (2hr)
  • step 3 initial temp 370 °C, rate (temp / hr) 47 °C / hr, temp (holdtime) 510 °C (3hr)
  • the sample is a modified conjugated diene-based polymer in which the solvent is removed by stirring in hot water heated with steam, and residual monomers, residual denaturants and oils are removed.
  • the N content may be measured through an NSX analysis method, for example, and the NSX analysis method may be measured using a trace amount nitrogen quantitative analyzer (NSX-2100H).
  • NSX-2100H a trace amount nitrogen quantitative analyzer
  • the trace nitrogen quantitative analyzer (Auto sampler, horizontal furnace, PMT & Nitrogen detector) is turned on, Ar 250 ml / min, O 2 350 ml / min, ozonizer 300 ml /
  • the carrier gas flow rate was set to min, the heater was set to 800 ° C. and then waited for about 3 hours to stabilize the analyzer.
  • a calibration curve with 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm ranges was prepared using the Nitrogen standard (AccuStandard S-22750-01-5 ml) to obtain an area corresponding to each concentration. A straight line was then created using the ratio of concentration to area.
  • a ceramic boat containing 20 mg of the sample was placed in an auto sampler of the analyzer and measured to obtain an area. The N content was calculated using the area of the obtained sample and the calibration curve.
  • the sample used in the NSX analysis method is a modified conjugated diene-based polymer sample in which a solvent is removed by stirring in hot water heated with steam and may be a sample from which residual monomer and residual denaturant are removed.
  • oil if oil is added to the sample, it may be a sample after the oil is extracted (removed).
  • the modified conjugated diene-based polymer may be a Mooney relaxation rate measured at 100 °C 0.7 or more, 0.7 or more 3.0 or less, 0.7 or more 2.5 or less, or 0.7 or more 2.0 or less.
  • the Mooney relaxation rate represents a change in stress that appears in response to the same amount of strain, and may be measured using a Mooney viscometer. Specifically, the Mooney relaxation rate is 27 ⁇ 3 g after leaving the polymer at room temperature (23 ⁇ 5 ° C.) for 30 minutes at 100 ° C. and Rotor Speed 2 ⁇ 0.02 rpm using a large rotor of Monsanto MV2000E. Sampling was performed by filling the inside of the die cavity and operating a platen to measure the Mooney viscosity while applying a torque, and then measuring the gradient value of the Mooney viscosity change appearing as the torque was released.
  • the Mooney relaxation rate can be used as an index of the branched structure of the polymer.
  • the Mooney relaxation rate decreases as the number of branches increases, so that the Mooney relaxation rate can be used as an index of the branching structure.
  • the modified conjugated diene-based polymer has a Mooney viscosity (Mooney viscosity) at 100 °C, 30 or more, 40 to 150, or 40 to 140, there is an excellent workability and productivity within this range.
  • Mooney viscosity Mooney viscosity
  • the modified conjugated diene-based polymer has a shrinkage factor (g ') determined by gel permeation chromatography-scattering measurement with a viscosity detector of 0.8 or more, specifically 0.8 or more and 3.0 or less, more specifically It may be 0.8 or more and 1.3 or less.
  • g ' shrinkage factor
  • the shrinkage factor (g ') determined by the gel permeation chromatography-photo scattering method measurement is a ratio of the intrinsic viscosity of the polymer having a branch to the intrinsic viscosity of a linear polymer having the same absolute molecular weight, It can be used as an index of the branching structure of a polymer, i.e. as an index of the proportion of branching, and for example, as the shrinkage factor decreases, the number of branches of the polymer tends to increase, thus comparing polymers having the same absolute molecular weight. In this case, the more branches, the smaller the shrinkage factor. Therefore, it can be used as an index of branching.
  • the shrinkage factor was calculated based on the solution viscosity and the light scattering method by measuring the chromatogram by using a gel chromatography-light scattering measuring device equipped with a viscosity detector, specifically, a column containing a polystyrene gel as a filler Using the GPC-light scattering measuring device equipped with two light-scattering detector and a viscosity detector to obtain the absolute molecular weight and the intrinsic viscosity corresponding to each absolute molecular weight, after calculating the intrinsic viscosity of the linear polymer corresponding to the absolute molecular weight , The shrinkage factor was determined by the ratio of the intrinsic viscosity corresponding to each absolute molecular weight.
  • the shrinkage factor is obtained by injecting a sample into a GPC-light scattering measuring device (Viscotek TDAmax, Malvern) equipped with a light scattering detector and a viscosity detector to obtain an absolute molecular weight from the light scattering detector, and from the light scattering detector and the viscosity detector to an absolute molecular weight.
  • a GPC-light scattering measuring device Viscotek TDAmax, Malvern
  • the intrinsic viscosity [ ⁇ ] 0 of the linear polymer with respect to the absolute molecular weight was calculated through Equation 2 below, and the ratio of the intrinsic viscosity corresponding to each absolute molecular weight ([ ⁇ ] / [ ⁇ ] 0 ) is represented by the shrinkage factor.
  • the eluent was mixed with 20 mL of a mixed solution of tetrahydrofuran and N, N, N ', N'-tetramethylethylenediamine (N, N, N', N'-tetramethylethylenediamine in 1 L of tetrahydrofuran).
  • Equation 2 M is the absolute molecular weight.
  • the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight.
  • the vinyl content may refer to the content of 1,2-added conjugated diene-based monomers, not 1,4-addition, based on 100% by weight of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer. Can be.
  • the modified monomer represented by the formula (1) according to an embodiment of the present invention may be one that can be introduced into the polymer chain while polymerizing with other monomers to form a polymer chain.
  • R 1 is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms , An alkoxyalkyl group having 2 to 20 carbon atoms or a phenoxyalkyl group having 7 to 20 carbon atoms.
  • X 1 and X 2 are each independently hydrogen or -O [CH 2 CH 2 O] a CH 3 , one of which is -O [CH 2 CH 2 O] a CH 3 , The other is hydrogen, and a may be an integer from 1 to 6.
  • Chemical Formula 1 may be a meta benzene ring substituted at 1 and 3 positions or a para benzene ring compound at 1 and 4 positions.
  • R 1 is hydrogen
  • X 1 and X 2 are each independently hydrogen or -O [CH 2 CH 2 O] a CH 3 , one of the two -O [CH 2 CH 2 O] a CH 3 , the other is hydrogen
  • a may be an integer from 1 to 6.
  • the modified monomer represented by Formula 1 is substituted or unsubstituted 3- or 4-hydroxy styrene and Z [CH 2 CH 2 O] a CH 3 such as acetonitrile It may be prepared by reacting in an organic solvent, wherein Z may be Cl or Br.
  • substituted or unsubstituted 3- or 4-hydroxystyrene and Z [CH 2 CH 2 O] a CH 3 may be reacted in a 1: 1 to 1: 2.5 molar ratio.
  • the modifier according to the present invention may be a modifier for modifying at least one end of the conjugated diene-based polymer, and may be a silica affinity modifier, for example.
  • the silica affinity modifier may mean a modifier containing a silica affinity functional group in a compound used as a modifier, the silica affinity functional group is excellent in affinity with the filler, in particular silica-based filler, It may mean a functional group capable of interaction between the functional group derived from the denaturant.
  • the aminoalkoxysilane-based modifier may be selected from compounds represented by the following Chemical Formula 2 or Chemical Formula 3.
  • R a1 and R a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms,
  • R a2 and R a3 are each independently an alkyl group having 1 to 10 carbon atoms
  • R a5 is a divalent, trivalent or tetravalent alkylsilyl group substituted with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms,
  • n 1 is an integer of 1 to 3
  • n 2 is an integer of 0 to 2
  • a 1 and A 2 are each independently an alkylene group having 1 to 20 carbon atoms
  • R b1 to R b4 are each independently an alkyl group having 1 to 20 carbon atoms
  • L 1 to L 4 are independently a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 10 carbon atoms.
  • the aminoalkoxysilane-based modifying agent may be a compound represented by Formula 2, wherein in Formula 2 R a1 and R a4 are independently of each other a single bond, or 1 to 5 carbon atoms
  • An alkylene group, R a2 and R a3 are each independently an alkyl group having 1 to 5 carbon atoms
  • R a5 may be a tetravalent alkylsilyl group substituted with a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms
  • n 1 may be an integer of 2 or 3
  • n 2 may be an integer of 0 to 2.
  • the compound represented by Formula 2 is N, N-bis (3- (dimethoxy (methyl) silyl) propyl) -methyl-1-amine (N, N-bis (3- (dimethoxy (methyl)) silyl) propyl) -methyl-1-amine), N, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine (N, N-bis (3- (diethoxy (methyl)) silyl) propyl) -methyl-1-amine), N, N-bis (3- (trimethoxysilyl) propyl) -methyl-1-amine (N, N-bis (3- (trimethoxysilyl) propyl) -methyl -1-amine), N, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine (N, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine), N, N-diethyl-3- (trimethoxysilyl
  • the aminoalkoxysilane-based modifying agent may be a compound represented by Formula 3, wherein in Formula 3 A 1 and A 2 are independently an alkylene group having 1 to 10 carbon atoms R b1 to R b4 are each independently an alkyl group having 1 to 10 carbon atoms, and L 1 to L 4 are independently substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Tetravalent alkylsilyl group.
  • the compound represented by Chemical Formula 3 is 3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine) (3,3 '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine)), 3,3'-(1,1,3,3 Tetraethoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine) (3,3 '-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine)), 3,3 '-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis (N, N-dimethylpropan-1-amine)), 3,3 '-(1,1,3,3
  • the polymer has a specific structure and may have a unique molecular weight distribution and shape.
  • the structure of the polymer may be expressed in physical properties such as shrinkage factor, Mooney relaxation rate, coupling number, the molecular weight distribution and its form may be expressed in the form of molecular weight distribution value and molecular weight distribution curve, and the number of coupling, Sodium end denaturation by denaturing agent and denaturing monomer can affect the structure, molecular weight distribution and shape. Parameters expressing the structure of such a polymer and characteristics related to the molecular weight distribution can be satisfied by the following production method.
  • the present invention also provides a method for producing the modified conjugated diene polymer.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared by the manufacturing method described below, so that the molecular weight distribution curve by gel permeation chromatography is unimodal, and the molecular weight distribution may be narrowed to 1.0 to less than 1.7.
  • the modified conjugated diene-based polymer may be excellent in workability and balance both tensile properties and viscoelastic properties.
  • Method for producing the modified conjugated diene-based polymer comprises a modified monomer, a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl monomer in the hydrocarbon solvent, in the presence of a polymerization initiator Polymerizing to prepare the active polymer into which the modified monomer-derived functional group is introduced (S1); And reacting or coupling the active polymer prepared in the step (S1) with the aminoalkoxysilane-based modifier (S2), wherein the step (S1) is carried out continuously in two or more polymerization reactors, and the polymerization
  • the polymerization conversion rate in the first reactor of the reactor may be 50% or less.
  • R 1 , X 1 and X 2 are as defined above, and the aminoalkoxysilane-based modifier is as described above.
  • the hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclo hexane, toluene, benzene, and xylene.
  • the polymerization initiator is not particularly limited, but for example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyl Lithium, phenyllithium, 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium Sodium naphthyl, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropy
  • the polymerization initiator is 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of the total monomers Can be used.
  • the total of 100 g of the monomer may be the total amount of the modified monomer and the conjugated diene monomer, or may represent the total amount of the modified monomer, conjugated diene monomer and aromatic vinyl monomer.
  • the modified monomer may be used in 0.001 g to 10 g compared to 100 g of the conjugated diene monomer, specifically 0.01 g to 10 g or 0.1 g compared to 100 g of the conjugated diene monomer To 10 g.
  • the polymerization of the step (S1) may be, for example, anionic polymerization, and specifically, may be living anion polymerization having an anion active site at the end of the polymerization by a growth polymerization reaction by anion.
  • the polymerization of the step (S1) may be an elevated temperature polymerization, an isothermal polymerization or a constant temperature polymerization (thermal insulation polymerization), and the constant temperature polymerization may include the step of polymerizing with the heat of reaction without adding any heat after the polymerization initiator is added.
  • the polymerization method may mean a polymerization method
  • the elevated temperature polymerization may mean a polymerization method in which a temperature is increased by optionally adding heat after adding the polymerization initiator, and the isothermal polymerization may be performed by adding heat after adding the polymerization initiator. It may mean a polymerization method of increasing the temperature or taking away the heat to maintain a constant temperature of the polymer.
  • the polymerization in the step (S1) may be carried out by further comprising a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, in this case, gel on the reactor wall surface for a long time operation It is effective to prevent this from being formed.
  • a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, in this case, gel on the reactor wall surface for a long time operation It is effective to prevent this from being formed.
  • the diene compound may be 1,2-butadiene.
  • the polymerization of the step (S1) may be carried out at a temperature range of 80 ° C or less, -20 ° C to 80 ° C, 0 ° C to 80 ° C, 0 ° C to 70 ° C, or 10 ° C to 70 ° C, for example.
  • a temperature range of 80 ° C or less 80 ° C or less, -20 ° C to 80 ° C, 0 ° C to 80 ° C, 0 ° C to 70 ° C, or 10 ° C to 70 ° C, for example.
  • the active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organic metal cation are combined.
  • the modified conjugated diene-based polymer manufacturing method may be carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and a modified reactor.
  • the step (S1) may be carried out continuously in two or more polymerization reactors including the first reactor, and the number of the polymerization reactors may be elastically determined according to the reaction conditions and environment.
  • the continuous polymerization method may mean a reaction process of continuously supplying a reactant to the reactor and continuously discharging the generated reaction product. In the case of the continuous polymerization method, it is excellent in productivity and processability and excellent in uniformity of the polymer to be produced.
  • the polymerization conversion rate in the first reactor may be 50% or less, 10% to 50%, or 20% to 50%, After the polymerization reactor is initiated within this range, it is possible to induce a polymer having a linear structure during polymerization by suppressing side reactions generated while the polymer is formed, and thus it is possible to narrowly control the molecular weight distribution of the polymer. The improvement is excellent.
  • the polymerization conversion may be adjusted according to the reaction temperature, the reactor residence time.
  • the polymerization conversion rate may be determined, for example, by measuring a solid concentration on a polymer solution containing a polymer when polymerizing the polymer.
  • a cylindrical container may be mounted at the outlet of each polymerization reactor. After filling the cylindrical solution with the positive polymer solution, and separating the cylindrical container from the reactor to measure the weight (A) of the cylinder filled with the polymer solution, the polymer solution filled in the cylindrical container was replaced with an aluminum container, As an example, the weight (B) of the cylindrical container, which is transferred to an aluminum dish and free of the polymer solution, is measured, the aluminum container containing the polymer solution is dried in an oven at 140 ° C. for 30 minutes, and the weight (C) of the dried polymer is measured. After the measurement, it may be calculated according to the following equation (1).
  • the polymerized in the first reactor is sequentially transferred to the polymerization reactor before the modification reactor, the polymerization may proceed until the polymerization conversion rate is at least 95%, and after the polymerization in the first reactor, the second reactor.
  • the polymerization conversion rate of each reactor from the second reactor to the polymerization reactor before the modified reactor may be carried out by appropriately adjusting the respective reactors to control the molecular weight distribution.
  • the polymer residence time in the first reactor may be 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes, within this range, polymerization It is easy to control the conversion rate, and thus it is possible to narrowly adjust the molecular weight distribution of the polymer, whereby there is an effect of excellent physical property improvement.
  • the term 'polymer' is carried out in each reactor during the step (S1), before the step (S1) or (S2) is completed to obtain an active polymer or a modified conjugated diene-based polymer. It can mean an intermediate in the form of a polymer being used, and can mean a polymer having a polymerization conversion of less than 95% in which polymerization is being carried out in the reactor.
  • the molecular weight distribution (PDI, polydispersed index; MWD, molecular weight distribution; Mw / Mn) of the active polymer prepared in step (S1) is less than 1.5, 1.0 or more to less than 1.5, or 1.1
  • the molecular weight distribution of the modified conjugated diene-based polymer prepared through the modification reaction or coupling with the modifier within this range may be less than or equal to 1.5, thereby improving the physical properties.
  • the polymerization of the step (S1) may be carried out including a polar additive
  • the polar additive is added in a ratio of 0.001g to 50g, 0.001g to 10g, or 0.005g to 0.1g based on a total of 100g monomer can do.
  • the polar additive may be added in a ratio of 0.001g to 10g, 0.005g to 5g, 0.005g to 4g based on a total of 1 mmol of the polymerization initiator.
  • polar additives examples include tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, and dimethyl ether.
  • Tertiary butoxyethoxyethane bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N, N, N ', N'-tetramethyl It may be at least one selected from the group consisting of ethylenediamine, sodium mentholate and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di (2-tetrahydro Furyl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate or 2-ethyl tetrahydrofurfuryl ether, the polar additive When including the effect of inducing a conjugated diene monomer and aromatic vinyl case of copolymerizing the monomers to compensate for differences in their reaction rates by giving to easily form a random copolymer.
  • the reaction or coupling of the step (S2) may be carried out in a modification reactor, wherein the denaturant may be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g monomer. .
  • the denaturant may be used in a molar ratio of 1: 0.1 to 10, 1: 0.1 to 5, or 1: 0.1 to 1: 3, based on 1 mole of the polymerization initiator in the step (S1).
  • the denaturant may be added to the modification reactor, the step (S2) may be carried out in the modification reactor.
  • the denaturant may be added to the transfer unit for transferring the active polymer prepared in the step (S1) to the modification reactor for performing the step (S2), and the mixture of the active polymer and the modifier in the transfer unit Reaction or coupling may proceed.
  • the modified conjugated diene-based polymer manufacturing method is a method that can satisfy the characteristics of the modified conjugated diene-based polymer described above, the effect to be achieved in the present invention as described above is In the above method, the polymerization conversion rate at the time of transferring from the first reactor to the second reactor under the continuous process needs to be satisfied, and in the case of other polymerization conditions, variously controlled, The physical properties of the modified conjugated diene-based polymer according to the present invention can be implemented.
  • the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
  • the rubber composition may include the modified conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and within this range, tensile strength, wear resistance, and the like. It is excellent in the mechanical properties of and excellent in the balance between each physical property.
  • the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition.
  • the other rubber component may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.
  • the rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene -Co-d
  • the rubber composition may include, for example, 0.1 part by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention.
  • the filler may be, for example, a silica-based filler, and specific examples may be wet silica (silicate silicate), dry silica (silicate anhydrous), calcium silicate, aluminum silicate, colloidal silica, and the like.
  • the wet silica may be the most compatible of the grip (wet grip).
  • the rubber composition may further include a carbon black filler as needed.
  • silica when silica is used as the filler, a silane coupling agent for improving reinforcement and low heat generation may be used together.
  • the silane coupling agent may include bis (3-triethoxysilylpropyl) tetrasulfide.
  • the compounding amount of the silane coupling agent is conventional.
  • the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight with respect to 100 parts by weight of silica, and the effect as a coupling agent is within this range. While sufficiently exhibiting, there is an effect of preventing gelation of the rubber component.
  • the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent.
  • the vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the rubber component, while ensuring the required elastic modulus and strength of the vulcanized rubber composition within this range while having low fuel efficiency. Excellent effect.
  • the rubber composition according to an embodiment of the present invention in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, antioxidants, plasticizers, anti-aging agents, anti-scorch agents, and zinc (zinc) white), stearic acid, a thermosetting resin, or a thermoplastic resin.
  • the vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG.
  • a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG.
  • Guanidine-based compounds such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.
  • the process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering the tensile strength and abrasion resistance, when the aromatic process oil, hysteresis loss and low temperature characteristics are considered.
  • Naphthenic or paraffinic process oils may be used.
  • the process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.
  • the antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis ((dodecylthio) methyl) -4-nonylphenol (2,6-bis ( (dodecylthio) methyl) -4-nonylphenol) or 2-methyl-4,6-bis ((octylthio) methyl) phenol (2-methyl-4,6-bis ((octylthio) methyl) phenol), 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the rubber component can be used.
  • the anti-aging agent is for example N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6-ethoxy-2 , 2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone, and the like, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.
  • the rubber composition according to an embodiment of the present invention may be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the formulation, and has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.
  • a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc.
  • the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.
  • the present invention provides a tire manufactured using the rubber composition.
  • the tire may include a tire or a tire tread.
  • the n-butyllithium solution dissolved in% was injected at a rate of 48.0 g / h, at which time the
  • a 1,3-butadiene solution in which 1,3-butadiene was dissolved at 60% by weight in n-hexane was injected into the second reactor at a rate of 2.95 kg / h.
  • the temperature of the second reactor was maintained at 65 °C, when the polymerization conversion rate was 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.
  • IR1520 BASF, Inc.
  • BASF, Inc. IR1520 solution dissolved at 30% by weight as an antioxidant in the polymerization solution discharged from the third reactor was injected and stirred at a rate of 167 g / h.
  • the resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.
  • Example 1 instead of 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1-amine as a modifier, N, N-bis (3- (diethoxy ( Same as Example 1 except that a solution in which methyl) silyl) propyl) -1,1,1-trimethylsilaneamine was dissolved at 20% by weight was continuously supplied to the third reactor at a rate of 103.5 g / h.
  • the modified conjugated diene-based polymer was prepared.
  • Example 1 instead of 1- (2-methoxyethoxy) -4-vinylbenzene as the modified monomer, 1- (2-methoxyethoxy) -3-vinylbenzene (1- Modification was carried out in the same manner as in Example 1, except that (2-methoxyethoxy) -3-vinylbenzene) was continuously supplied to the first reactor at a rate of 89.0 g / h of a modified monomer solution in which 15 wt% was dissolved. A conjugated diene polymer was prepared.
  • the prepared n-butyllithium solution was injected at a rate of 48.0 g / h. At this time, the temperature of the first reactor was maintained at 55 ° C., and when the polymerization conversion rate reached 48%, The polymer was transferred from the reactor to the second reactor.
  • IR1520 BASF, Inc.
  • 30% by weight of an antioxidant into the polymerization solution discharged from the second reactor was injected and stirred at a rate of 100 g / h.
  • the resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare an unmodified conjugated diene polymer.
  • the prepared n-butyllithium solution was injected at a rate of 48.0 g / h, at which time the temperature of the first reactor was maintained at 50 ° C., and when the polymerization conversion ratio reached 43%, The polymer was transferred from the reactor to the second reactor.
  • a 1,3-butadiene solution in which 1,3-butadiene was dissolved at 60% by weight in n-hexane was injected into the second reactor at a rate of 2.95 kg / h.
  • the temperature of the second reactor was maintained at 65 °C, when the polymerization conversion rate was 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.
  • the polymer was transferred from the second reactor to the third reactor, and 64.0 g / h of a solution in which 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1-amine was dissolved at 20% by weight as a modifier.
  • To the third reactor at a rate of.
  • the temperature of the third reactor was maintained at 65 ° C.
  • IR1520 BASF, Inc.
  • BASF, Inc. IR1520 solution dissolved at 30% by weight as an antioxidant in the polymerization solution discharged from the third reactor was injected and stirred at a rate of 167 g / h.
  • the resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene polymer.
  • Example 1 when the polymerization conversion rate was 43%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe, and 3- (dimethoxy (methyl) silyl) -N, Same as Example 1 except that a solution in which dichlorodimethylsilane was dissolved in 2% by weight in n-hexane instead of N-diethylpropan-1-amine was added to the third reactor at a rate of 36 g / h. The modified conjugated diene-based polymer was prepared.
  • Example 3 the reaction temperature was maintained at 75 ° C. in the first reactor, 80 ° C. in the second reactor, and 80 ° C. in the third reactor, and when the polymerization conversion rate reached 70% in the first reactor, In the same manner as in Example 3, except that the polymerization product was transferred from the first reactor to the second reactor, the modified conjugated diene-based polymer was prepared.
  • Comparative Example 1 a modified conjugated diene system was performed in the same manner as in Comparative Example 1 except that 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1-amine was added at 16.5 mmol. The polymer was prepared.
  • Comparative Example 1 a modified conjugated diene system was carried out in the same manner as in Comparative Example 1 except that 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1-amine was added at 2.5 mmol. The polymer was prepared.
  • Styrene unit content vinyl content, weight average molecular weight (Mw, X10 3 g / mol), and number average molecular weight of each modified or unmodified conjugated diene-based polymer prepared in Examples, Comparative Examples, and Reference Examples, respectively, Mn, X10 3 g / mol), molecular weight distribution (PDI, MWD), coupling number, Mooney viscosity (MV), Mooney relaxation rate, shrinkage factor and Si content and N content were measured, respectively. The results are shown in Table 1 below.
  • styrene unit (SM) and vinyl (Vinyl) content in each polymer was measured and analyzed using Varian VNMRS 500 MHz NMR.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by GPC (Gel permeation Chromatography) analysis to obtain a molecular weight distribution curve.
  • molecular weight distribution (PDI, MWD, Mw / Mn) was calculated and obtained from each said measured molecular weight.
  • the GPC uses a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) columns and the GPC standard material is PS (polystyrene) when calculating the molecular weight. It was carried out using.
  • GPC measurement solvent was prepared by mixing 2% by weight of an amine compound with tetrahydrofuran. At this time, the obtained molecular weight distribution curve is shown in Figs.
  • the coupling number is obtained in each of the Examples, Comparative Examples and Reference Examples before the addition of the modifier or coupling agent to obtain a peak molecular weight (Mp 1 ) of the polymer to obtain a peak molecular weight of each modified conjugated diene-based polymer (Mp 2 ) was obtained and calculated by the following equation.
  • the Mooney viscosity (MV, (ML1 + 4, @ 100 °C) MU) was measured using a Rotor Speed 2 ⁇ 0.02 rpm, Large Rotor at 100 °C using MV-2000 (ALPHA Technologies) Samples were allowed to stand at room temperature (23 ⁇ 3 ° C.) for at least 30 minutes, and then collected 27 ⁇ 3 g, filled into the die cavity, and platen operated for 4 minutes.
  • the Si content was measured using an inductively coupled plasma luminescence analyzer (ICP-OES; Optima 7300DV) by the ICP analysis method. Specifically, about 0.7 g of the sample is placed in a platinum crucible, about 1 mL of concentrated sulfuric acid (98 wt%, Electronic grade) is heated at 300 ° C. for 3 hours, and the sample is heated in an electric furnace (Thermo Scientific, In Lindberg Blue M), the conversation is carried out using the program of steps 1 to 3 below.
  • ICP-OES inductively coupled plasma luminescence analyzer
  • step 1 initial temp 0 °C, rate (temp / hr) 180 °C / hr, temp (holdtime) 180 °C (1hr)
  • step 2 initial temp 180 °C, rate (temp / hr) 85 °C / hr, temp (holdtime) 370 °C (2hr)
  • step 3 initial temp 370 °C, rate (temp / hr) 47 °C / hr, temp (holdtime) 510 °C (3hr)
  • N content was measured using an NSX analysis method, a trace amount nitrogen quantitative analyzer (NSX-2100H). Specifically, the carrier gas flow rate is set to 250 ml / min for Ar, 350 ml / min for O 2 and 300 ml / min for ozonizer, with the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) turned on. Was set at 800 ° C. and then waited for about 3 hours to stabilize the analyzer.
  • NSX-2100H a trace amount nitrogen quantitative analyzer
  • a calibration curve with 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm ranges was prepared using the Nitrogen standard (AccuStandard S-22750-01-5 ml) to obtain an area corresponding to each concentration. A straight line was then created using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample was placed in an auto sampler of the analyzer and measured to obtain an area. The N content was calculated using the area of the obtained sample and the calibration curve.
  • the shrinkage factor was injected into a GPC-light scattering measuring instrument (Viscotek TDAmax, Malvern) equipped with a light scattering detector and a viscosity detector to obtain an absolute molecular weight from the light scattering detector, and an intrinsic viscosity of the absolute molecular weight from the light scattering detector and the viscosity detector [ ⁇ ],
  • the intrinsic viscosity [ ⁇ ] 0 of the linear polymer with respect to the absolute molecular weight is calculated through the following equation (2), and the ratio of the intrinsic viscosity corresponding to each absolute molecular weight ([ ⁇ ] / [ ⁇ ] 0 ) is obtained.
  • the mean value is shown as a shrinkage factor.
  • the eluent was mixed with 20 mL of a mixed solution of tetrahydrofuran and N, N, N ', N'-tetramethylethylenediamine (N, N, N', N'-tetramethylethylenediamine in 1 L of tetrahydrofuran).
  • Equation 2 M is the absolute molecular weight.
  • Modified monomer M2 1- (2-methoxyethoxy) -3-vinylbenzene
  • Modifier F1 3- (dimethoxy (methyl) silyl) -N, N-diethylpropan-1-amine
  • Modifier F2 (N, N '-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis (propane-3,1, -diyl) bis (1,1,1-trimethyl -N- (trimethylsilyl) silaneamine)
  • Modifier F3 N, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1,1-trimethylsilamine
  • the modified conjugated diene-based polymer of Examples 1 to 4 has a unimodal form of the molecular weight distribution curve by gel permeation chromatography (FIG. 1).
  • the molecular weight distribution (PDI) is 1.0 or more and less than 1.7
  • the Si content and the N content are more than 50 ppm
  • the Mooney relaxation rate is 0.7 or more
  • the shrinkage factor is 0.8 or more.
  • the unmodified or modified conjugated diene-based polymers of Comparative Examples 1 to 5 have a bimodal form in the molecular weight distribution curve by gel permeation chromatography (see FIG.
  • Mooney relaxation ratio is less than 0.7
  • shrinkage It can be seen that the factor is less than 0.8, the Si content is less than 50 ppm or the N content is less than 50 ppm, especially prepared by continuous polymerization, but the polymerization conversion rate in the first reactor is out of the scope of the present invention Comparative Example 5 It can be seen that the PDI value exceeds 1.7 and the Mooney relaxation rate and shrinkage factor are 0.517 and 0.488, respectively, which are less than the numerical ranges presented in the present invention and are significantly reduced compared to the examples.
  • the modified conjugated diene-based polymers of Comparative Examples 3 and 4 are prepared at the same level as in the embodiment according to the present invention except for the application of the modified monomer during polymerization and the type of the modifying agent, the molecular weight distribution, the number of coupling, Polymer physical properties such as Mooney relaxation rate and shrinkage factor showed similar levels as in Example, but did not include a modified monomer-derived functional group or a denaturant-derived functional group, and thus poor filler affinity, which is compared in Table 3 below. It can be confirmed that the tensile properties and viscoelastic properties of Examples 3 and 4 are significantly reduced compared to the examples.
  • Each modified or unmodified conjugated diene-based polymer of Examples, Comparative Examples and Reference Examples was blended under the blending conditions shown in Table 2 below as raw rubber.
  • the content of raw materials in Table 2 is each part by weight based on 100 parts by weight of raw rubber.
  • the rubber specimen is kneaded through the first stage kneading and the second stage kneading.
  • a half-barrier mixer equipped with a temperature control device is used to make raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zincating agent (ZnO), stearic acid.
  • TMQ Antioxidant
  • RD (2,2,4-trimethyl-1,2-dihydroquinoline polymer)
  • antioxidant (6PPD ((dimethylbutyl) -N-phenyl-phenylenediamine)
  • wax Merocrystaline Wax
  • the primary compound was cooled to room temperature After that, the primary blend, sulfur, rubber accelerator (DPD (diphenylguanine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and the temperature was 100 ° C. or lower.
  • a second blend was obtained by mixing in. Then, a rubber specimen was prepared by a curing process at 160 ° C. for 20 minutes.
  • Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the specimen and the tensile stress (300% modulus) at 300% elongation. Specifically, the tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.
  • Viscoelastic properties were determined by measuring the viscoelastic behavior for dynamic deformation at 10 Hz frequency and each measurement temperature (-60 °C ⁇ 60 °C) in the film tension mode using a dynamic mechanical analyzer (GABO).
  • GBO dynamic mechanical analyzer
  • the result is expressed as an index based on the result of Comparative Example 2, the higher the value, the better.
  • each secondary blend was left at room temperature (23 ⁇ 3 °C) for 30 minutes or more 27 ⁇ 3 g was taken and filled into the die cavity and platen operated for 4 minutes.
  • Examples 1 to 4 according to an embodiment of the present invention is improved in tensile properties, viscoelastic properties and workability properties compared to Comparative Examples 1 to 5.
  • Examples 1 to 4 exhibited reduced workability compared to Comparative Example 2, which is an unmodified conjugated diene-based polymer, but exhibited excellent tensile properties of 300% modulus of 30% or more, and improved tan ⁇ at 0 ° C. While showing the value, the tan ⁇ value at 60 ° C. was significantly increased to 25% or more.
  • Examples 1 to 4 exhibited the same or more workability, tensile properties, and tan ⁇ at 0 ° C., while the tan ⁇ at 60 ° C. was significantly improved to about 10% or more. Indicated.

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CN114929765A (zh) * 2020-08-05 2022-08-19 株式会社Lg化学 改性共轭二烯类聚合物和包括其的橡胶组合物
US20230108559A1 (en) * 2020-10-12 2023-04-06 Lg Chem, Ltd. Oil-extended modified conjugated diene-based polymer, method for preparing same and rubber composition comprising same
CN113185639B (zh) * 2021-04-29 2023-04-21 四川大学 一种高强度低松弛聚异戊二烯橡胶及其制备方法

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